Alkylation of paraffin hydrocarbons



ALKYLATIQN Filed July 24, 1942 v FRESH Y H. c. MAYLAND OF PARAFFIN HYDROCARBONS 2 Sheets-Sheet 1 2 Sheets-Sheet 2 H. c. M AYLAND Filed July 24, 1942 ALKYLATION OF PARAFFIN HYDROCARBONS July 23, 194e.

Patented July 23, 1946 ALKYLATION OF PARAFFIN HYDROCARBONS Harrison C. Mayland, Chicago, Ill., assignor to Universal Oil Products Company, a corporation of Delaware Chicago, Ill.,

Application July 24, 1942, Serial No. 452,122

6 Claims. l (Cl. 26g-683.4)

This invention relates to the alkylation of hydrocarbons in the presence of a hydrogen uoride catalyst.

It is more particularly concerned with an improved process for the production of higher molecular weight isoparains by the alkylation of lower boiling isoparaflins with oleflns in the presence of a hydrogen fluoride catalyst wherein the concentration of hydrogen fluoride is controlled within a preferred range in order to obtain the optimum product quality.

The production of higher molecular weight isoparafdns having valuable anti-knock properties and therefore suitable for use in aviation fuels is of considerable importance in the refining industry. A convenient source of such hydrocarbons is the catalytic alkylation of low boiling isoparaii'ins such as isobutane and isopentane with normally gaseous olefins such as propylene and the butylenes. Large quantities of these hydrocarbons are available from the cracking of petroleum oils and from the natural gasoline industry.

The alkylation of isoparaflins utilizing a liquid l catalyst, such as hydrogen fluoride, is ordinarily conducted by introducing the hydrocarbon charging stock and catalyst into a mechanically agitated reaction Zone or any reaction zone suitable for effecting intimate contact between the hydrocarbons and catalyst. The hydrocarbon-catalyst mixture is maintained at the desired temperature, pressure, and time of contact, and it is preferable that a substantial molecular excess of isoparaffins over olefins be maintained throughout the entire reaction. The reaction mixture is withdrawn and is introduced into a separation zone which ordinarily will comprise a settler. The lower used catalyst layer is recycled from the settler to the reaction zone, a portion thereof being preferably withdrawn from the system and introduced into a catalyst regeneration zone. T he upper hydrocarbon layer from thersettler is subjected to fractionation for the recovery of gasoline boiling range products and for the separation 'of unconverted isoparaffins which may be recycled to the reaction zone.

When hydrogen fluoride catalysts are used to effect alkylation, certain organic materials are formed in addition to the alkylation products 0f the reaction which tend to accumulate in the catalyst phase and which serve effectively as 'organic diluents for the catalyst. The nature of the organic diluent formed in the alkylation reaction is not known clearly, but it is believed that in some cases at least higher molecular Weight alkyl fluorides, particularly those having 6 or more carbon atoms per molecule, are present as well as highermolecular weight -polymers and organic fluorine-containing complexes. y

As the alkylation reaction is conducted ccntinuously with recycling of the separatedused catalyst, a substantial portion of the organic diluent formed remains dissolved or dispersed in the catalyst phase and is therefore continuously recycled within the system. It is thus possible for the organic diluent content of thecatalyst to build up with continued use and the effective hydrogen fluoride concentration is thereby reduced.

Myinvention contemplates controlling the ac.- cumulation of organic diluent in thecatalyst phase by any convenient method of control whereby to vcontain the effective hydrogenfluoride concentration within the most desirable range as hereinafter described. One method of controlling the accumulation ofv organic diluent comprises withdrawing a portion of the used catalyst from the system and replacing itwith relatively uncontaminated catalyst such as fresh hydrogen fluoride or regenerated catalyst having a higher effective concentration of hydrogen fluoride.

Although under some alkylation conditions using a mineral acid catalyst such as sulfuric acid or hydrogen fluoride, itis desirable to maintainv the acid concentration as high as possible, e. g.,

by utilizing the highest acid replacement rate,`

that is economically feasible, I have' now found that good results may be obtained at relatively low acid concentrations when using a hydrogen fluoride catalyst. I have further discovered that in many cases improved results may loe-obtained by controlling the hydrogen iiuoride dilution Within a relatively critical range wherein the optimum quality of alkylation products is obtained.

In one specific embodiment my invention comprises an improvement' in thealkylation of isoparaflins with olens in the presence of a hydrogen fluoride catalyst wherein the hydrocarbon reaction products are separated from the used `catalyst, said separated hydrocarbon reaction products are subjected to fractionation, at least a portion of 'said used catalyst is returned to the i alkylation zone, and used catalyst is withdrawn 1 from the system and replaced with catalyst hav- 1 ing a higherreffectiveconcentrationgof'hi/drogen.; iluOride, saidiirhprovement comprising-the step'- lof controlling the withdrawal of used catalyst and the addition of more concentrated hydrogen :uoride whereby to maintain the concentration of hydrogen fluoride in the catalyst phase'within..

the range wherein alkylation products of optimum quality are obtained.

In Fig. 1 is shown a schematic; flow 'diagram'v` `of the type of alkylation process to which my'- invention is related.

Fig. 2 illustrates graphically the limitations on ,the useful degree of the dilution of thecatalyst phase.

Referring. to-Fig. f1; a..1r.esh`.hydrocarbon` feed comprisingja-eparaiiin-.olenmixture: wherein isoparains area preferably;v present in substantial molar.- excessover. the: oleI-lns-` is introduced through-.lined into alkylation zone 2.. This zonemay; comprise-any;y convenient arrangement. of

equipment.orapparatus,capable. of effecting-intimate: contacting;l ofv the? hydrocarbon reactants.

and. catalyst. A-.fresh.. liquid hydrogen uoride catalyst yis introduced throughline .3, Alkylation` zonef2:is..preferably operatedat apressure such that .-.the catalyst. andhydrocarbons. are.- maine' tained substantially in. the-liquid phase..

The reaction Amixture :passes .through line A into separationzone 5 .which may conveniently com7 prise. a.. settling.. zone; catalyst-is removedmthrough line I 6 and introducedin part-.into regeneration zone..7. A substantial.; portion of.. the. used hydrogen fluoride catalyst-removed throughline 6 is recycled' by means of line 8'to the alkylationY zone. 2. generationzone. 1 may comprise any4 eiective means;eg;, aheating 'or' distillationzone; whereby puried hydrogen uoride may be separated from the organic contaminants present' in the used: catalyst: Water may also be rerlrioved'fron'il the` used acid' in this zone.` Theregenerated acid'is-tI''en-WithdraWn to' storage through line IUT-or lmay berecycled through line` l l vtothe alkylatinzone. The organiccontaminants or re' sidua-lmaterial which remain after the recovery Used. hydrogen fluoride.

is used throughout this speci'cation and appended claims, it lis intended to include catalysts wherein hydrogen uoride is the essential active ingredient. Thus it is Within the scope of my invention to employ catalysts containing relatively minor amounts of other materials in addition to hydrogen fluoride. For example, the hydrogen iluoride catalyst may contain minor quantities of Water. While ordinarily commercial anhydrous hydrogen uorde will be charged to the alkylation system, it is possible to have as high as about 10 to 15% waterpresent in the catalyst.- Excessive dilution with Water, however, is undesirable since it tends to reduce the alkylating activity of lthe catalyst. Other substances such as :boronptriuoride whichigmay promotefthe catalytic activity of hydrogenI fluoride in" alkylation reactions may also be present.

The alkylation of isoparainns with olens in thepresence vof a hydrogen uoride catalyst may beLconducted' at a temperature of from about 0 F., to about 200 F., although the reaction temperature is preferably and more conveniently heldwithin -the range of from about 50 F., to about 150 F.' Thepressure on the alkylation systemisordinarily just high enough to insure Cil of purified hydrogenlilu'oride xfrom lthe 'used' catalystiare withdrawn from theI regeneration zonethr'oughlline 9.1 y

The '-sep'aratedhydrocarbon phase passes :from zone-5 bysmeans of line `rl2.ir1to lfractionation zone I3. Light hydrocarbon gases of the process are recoveredihroughlline: I8.-` A low'boiling unconvertedfzisoparaiiin. stream' .suchf .asl isobutaneY may befre'coveredz' throughline M- and'is preferably Y recycled; by. means ofiline; I5: to -alkylation-zonef f 21;. SaturatedM gasoline boiling; range hydrocar bonsiaresremoved through linel 6, and the :higheri boiling hydrocarbon reaction .products are recoveredthrough. line .-I 7.

Bythe-termhydrogen uoride eatalyst. which 5 that thehydrocarbons and catalyst are substantially the liquid phase. The reaction may be subjected to further control by means of the space -time -which isdenedas' thevolume. ,offcatalystA within the. contacting Zone divided by, the volume rate 10er minute of hydrocarbon-react-v ants charged to the zone. Usually thespace--time Willlie Within the .range of from.about 5 -to about minutes, although; this irange may inv certain" cases be-extended :in either direction. Itis-prei.-` erable-to maintain atall. timesA a-` substantial.. molarexcess of.isoparafnsover olens-in thealkylation'zone, -e;.g., from 4-:1 to 10:1 .or higher.-

The alkylation of isoparalinswvitholens,utilizing hydrogen iluoride-.catalysts is, particularly important in: the.- case-v of'. the :alkylation ..of'"iso butane with.norrnally gaseous olensf such asV propylenefor. butylene which are readily; availeable-insubstantial quantities. fromordinary ref lining 4sources.. However; kthe process-.may `also l.be` applied. .to normallyv liquid .isoparaiiinsandznorf mally liquid .olens It .is..also.zpossibleI to. employ mixtures of the normally liquid andnormally gaseous hydrocarbons as reactants.

The .term crude alkylate? as `.used in .this specification is` intended to designate the totalstaf bilized: hydrocarbonY reaction products.- ofA the process; and it thus. includes. not-:only ,thegavia-tion' gasoline fraction .but also the higherboihngprod.- uctsof V,the .reaction.

To illustrate more definitely the-natureofmy` invention I nowrefer tothefollowingtable-which:l

includes experimental. data obtained in twelvealkylationv runsl using, a substantially anhydrous hydrogen uoride. catalyst and. a hydrocarbon. charging stock. having the --followingapproximate molall composition: 4%. isobutylene,. 9%. n.bu

nots, vmeans for. recycling the usedcatalyst .from;

the settling zone to thereaction zonefand .mea-ns.-

for'withdrawing a portion of the used catalyst from the system.

6 such as space time, temperature, composition of the fresh charging stock and the combined feed,

Run No.

Series.. A B C 0. 1. 7 0. 0 l. 7 1. 3 4. l 3. 8 4. 1 3. 8 4. 1 9. 3 9.1 9. 3 9.1 8.7 i-Clllm 70. 0 69. 3 70. 0 69. 3 69. 7 n-C4H1o.. 15. 9 15. 3 15.9 15. 3 15.6 05+ 0.7 0. 8 0. 7 0.8 0.6 i-Parain/oleiu ratio 5. 2 5. l 5. 2 5. 1 5. 3 Conditions: l l i l Space time, mim... 36 35 36 36 61 54 53 50 9 1l 12 l1 Press., p. s. i. gage.. 150 Temp., 100 50 Vol. ratio, catalyst/hydrocarbon, 1n reaction zone. 1. 1 l. 2 1. 0 1.1 1. 4 1. 0 1.1 1.0 0.9 1. 2 1.4 1. 2 Catalyst withdrawal rate, cc./hr 12.1 8. 4 3.1 1. 2 2. 4 1. 9 1.1 0. 9 96. 6 4l. 4 13. 3 9. 5 Catalyst addition rate, cc./h 20. 0 6. 0 5.5 3. 3 7. 2 4.0 3. 0 310 102.0 48.0 16.0 11. 0 R. P. M. of agitator in contacting zon 1750 3500 Analysis of catalyst phase:

Total titratable acidity, wt. per cent 86. 8 81.1 73. 2 66. 6 85.3 76. 7 72. 9 69.4 92. 1 88. 7 79. 5 73.1 Water, wt. per cent 2. 6 2.0 1. 9 4. 0 2. 7 1.0 1.1 1.1 1.2 1.2 l. 2 1. 2 R l(1)1rganic diluent, wt. per cent 11.1 16.9 24. 9 29. 4 12.0 22. 3 26. 0 29. 5 6. 7 10.1 19.3 25. 7

es ts:

A. S. T. M. Octane No. 0f 275 F. E. P. a1ky1ate. 92. 3 92. 7 92. 9 92.1 91.4 92. 7 92.4 92. 4 92.3 92. 5 92.7 92. 3 Vol. crude alkylate/vol. catalyst withdrawn 22 30 84 198 60 91 162 176 7 18 56 66 Vol. 275 F. E. P. alkylate/vol. catalyst withdrawn 20 27 75 171 54 82 144 153 7 17 51 58 Bronline No. of crude alkylate r 0.1 0.1 0.1 0.2 0.1 0.1 0.2 0.1 0. 1 0.1 0. l

Series A comprising runs 1, 2, 3 and 4 was made at 100 F., 36 minutes space time and 1750 R. P. M.

on the mechanical agitator in the reaction zone. In series B comprising runs 5, 6, 7 and 8 the space time was .increased to an average value of about minutes with all other conditions the same. Series C comprising runs 9, 10, 11 and 12 was made at 50 F., an average space time of about 11 minutes, and 3500 R. P. M. on the mechanical agitator. The four tests in each series were made at decreasing values of total titratable acidity in the catalyst phase in order to illustrate the effect of the hydrogen fluoride concentration under each set of conditions.

It can be seen by examining the data for each series that as the total titratable acidity of the catalyst phase in the reaction system decreases, the volume of crude alkylate produced per volume of used catalyst withdrawn from the system increases markedly. Substantially the same effect is noted in terms of volumes of 275 F., E. P. alkylate produced per volume of used catalyst withdrawn from the system. It is apparent, then, that a considerable economic advantage accrues by operating at a relatively low titratable acidity since the quantity of desired product obtained at a given hydrogen fluoride replacement rate or a given hydrogen fluoride regeneration cost is substantially improved. l

However, I have found as a result of experimental tests that there are limitations on the useful degree of the dilution of the catalyst phase since with too great a dilution the quality of the product is adversely affected. This fact is illustrated in Fig. 2 wherein the Weight per cent total acidity of the catalyst phase has been plotted against the A. S. T. M. octane number of the 275 F., E. P. alkylate product for all three series. It will be seen that for each of the three series there is a denite optimum range of total acidity wherein the highest octane number product is obtained.

It is not possible to establish definitely a relatively narrow range of total acidity which will give optimum results in all cases. The exact optimum range for any case may depend to a considerable extent on the other process variables degree of mixing of reactants and catalyst, water content ofthe catalyst, etc. The effect on the location of the optimum acidity range caused by changing other process variables may be illustrated by comparing the curves for series A and B which were made at space times of 36 and 55 minutes, respectively. The .major effect under the conditions of the two series was merely a general decrease in the octane number level of the product, as the space time was increased over the range of 36 to 55 minutes. However, in the case of series C the space time was decreased, the temperature was decreased, and the degree of mixing (as a function of the agitator speed) was increased with Vthe net result that the optimum range of total acidity was definitely displaced in the direction of higher hydrogen fluoride concentrations. In practical terms this means a higher regeneration rate or catalyst replacement rate is required.

While it is thus not possible to establish they e. g., when alkylating isobutane with propylene,`

butylenes, or amylenes, the desirable total acidity will fall within the broader range of from about to about 95%. Moreover, when'isobutane is alkylated with normally gaseous oleiins in the presence of a hydrogen fluoride catalyst under substantially liquid phase conditions and at temperatures of from about 50 F., to about 100 F., or slightly higher, the optimum octane number products will be obtained at a total acidity within the range of from about to about 85%.

It should be noted that the titratable acidity of the catalyst phase within the reaction system is an eective measure of the free hydrogen fluoride concentration. However, it is not necessarily a true measure of the catalytic activity of the catalyst phase unless the complete composition of the phase is known. From the data obtained in these runs, it will be seen that the dilution of the hydrogen fluoride was accomplished largely by the accumulation of organic diluent during the process vwill be of the commercially anhydrous variety which contains several per cent of water, under certain 'conditions 'somewhat larger amounts of water may be present as hereinbefore described. This, of course, may eiect the location of the critical rangeV of Ytotal acidity. Previous experienceV has shown that hydrogen uoride diminishes greatly in its alkylation activity if more than from about 10% to about 15% Water is present. From the data presented here it is evident that substantially larger amounts of organic-diluent formed. duringthe alkylation reaction may be present in many cases without an adverse effect on the catalyst activity.y y

Althoughthe mechanism ofthe effect of controlled amounts of organic diluent in the catalyst phase is not entirely clearit'appears that the catalyst activity isl altered by the presence of the organic material to such` an extent that undedesirableside reactions are repressed resulting in improvedquality of the alkylation-products,4 said improved quality being evidenced,` for eX- Y ample, by the'relatively high octane number. It

isnot intended, however; that the scope oi-.my

invention be limited in any way by this explana-y tion of the effect of the organic diluent.

Eromexperimental observations I have 1 shown that unexpectedmesultsmay be'obtained in the alkylation of isoparains: with olens using. a hydrogen fluoride'cata1yst` of relatively high vorganic diluenticontent; This is contrary to previous experience with mineral. acidialkylation catalysts, sinceit:would'ordinarily be4 expected that the product;qualityVl would decline` continuously with increasing*contaminationofthel catalyst. I have not onflyshownthat good resultscan'be obtained withvhydrogenfluoride catalysts of relatively low titratable aciditiesbut Athat under-any` given set of processing conditions there s yalso arelatively Whilein;most instances the hydrogeniiiuoride charged 4to the falkylation.

criticalV range of totalY acidity whichmust not i be-exceededv if products-*of optimum vquality are to;be.obtained.

I;claim asmyinvention:

1;v An alkylation-process whichY comprises rel actingranfisoparamn with anolenin the pres- 1 ence of aY substantially anhydrous hydrogen v fluoride catalyst', thereby. forming a 'catalyst y phase;.containingf--organic diluent of higher molecular weight .than the alkylated isoparafm andv n] controlling; the. r accumulation. of: said, organic diluent in the. catalystiphase to maintain the hydrogen uoride.- concentration ofgthe catalyst l phasefwithinV the range of'fromeabout 703to about l rweightg'percent.

'i 2.; Anv alkylation processi.,-which.comprscsner4 acting an isoparaiin with an olensinztheefpresv ence of a substantially anhydrous hydrogenv iluoride catalyst, thereby Vforming a catalyst phase containing organic diluent of higher molecular weight than the alkylated isoparan, withdrawing used catalyst from and adding more concentrated hydrogen fluoride to the alkylatingf.

step, and, by regulation of saidV catalyst .withdraWal and addition, controlling the accumulation of said organic diluent in the catalyst phase to maintain the hydrogen nuoride concentration ofthe catalyst phase within the range oflfrom .about to about 85 weight percent.

`3. The process as defined in claim 2 further characterized in that the `withdrawn used cata:-

lyst is regenerated to separatehydrogen'uoride from organic diluent and the former returned to the alkylatingstep vas at least a portionof-'said more concentrated hydrogen Euclide.

4. An alkylation process which comprisesrel acting isobutane with a normally gaseous olefin at a temperature of from about 50F. 'to about 100 F. in the presence of a substantially anhye.

drous hydrogen fluoride catalyst,l thereby forming a catalyst phasecontaining o-rganic diluent of higherV molecular weight vthan the alkylated isobutane, and controlling the accumulationY of said organic diluent. inthe lcatalystv phase;` to

maintain the titratable'acidityfoff the catalyst;

about"` phase within the range-of from about .'70fto weight percent.y

catalyst withdrawal and addition, ,controllingtlie accumulation of said'organicfdiluent inthe cat'- f alystphase to maintain; the titratableracidityfof. the catalystv phase within', theA range; off' fromabout 70 to about .85.Weight percent:

6. The process as 'deiined inclaimy 5 further" characterizedin that the withdrawn vusedlcatat lystis regenerated to separate hydrogenffluoridelfrom'organic diluent and thelformer"returnedfto the alkylating'stepas at leasta portioniofrsaidZ more concentrated hydrogen fluoride;

HARRISON C'." 

